SB 

ess 

T^5 



U. S. DEPARTMENT OF AGRICULTURE 

BUREAU OF PLANT INDUSTRY— BULLETIN NO. 235. 

I ' \.Ui\VA\, Chief of Bureau. 



WILD VOLATILE-OIL PLANTS AND THEIll 

ECONOMIC IMPORTANCE: I.-BLACK SAGE; 

IL-WILD SAGE; III.-SWAMP BAY. 



FRANK KAP.AK, 

Chemical Biologist, Drug-Plant , Foisonous-Plant , Physiological, 
and Fermentation Investigations. 



T>.srKi) .Tantakv ?A), 1912. 




WASHINGTON: 

GOVKRNMENT PRTNTING OFFICK. 

1912. 




Glass SJB x^S 

Book__ T^3 



^ 



U. S. DEPARTMENT OF AGRICULTURE. 

BUREAU OF PLANT INDUSTRY— BULLETIN NO. 235. 

B. T. GALLOWAY, Chief of Bureau. 



WILD VOLATILE-OIL PLANTS AND THEIR 
ECONOMIC IMPORTANCE: I.-BLACK SAGE; 
IL-WILD SAGE; III -SWAMP BAY. A /^ y 



^7 



FRANK RABAK, 

Chemical Biologist, Drug-Plant, Poisonous-Plant, Physiological, 
and Fermentation Investigations. 



Issued January 30, 1912. 




WASHINGTON: 

OOVERNMENT PRINTING OFFICE. 

1912. 



Crjc^ h 



^^ 






BUREAU OF PLANT INDUSTRY. 



Chief of Bureau, Beverly T. Galloway. 
Assistant Chief of Bureau, William A. Taylor. 
Editor, J. E. Rockwell. 
Chief Clerk, James E. Jones. 



Drug-Plant, Poisonous-Plant, Physiological, and Fermentation Investigations. 

scientific staff. 

Rodney H. True, Physiologist in Charge. 

A. B. Clawson, Heinrich Hasselbring, C. Dwight Marsh, and W. W. Stockberger, Physiologists. 

James Thompson and Walter Van Fleet, Experts. 

Carl L. Alsberg, H. H. Bartlett, Otis F. Black, H. H. Bimzel, Frank Rabak, and A. F. Sievers, 

Chemical Biologists. 
W. W. Eggleston, Assistant Botanist. 

S. C. Hood, G. F. Mitchell, and T. B. Young, Scientific Assistants. 
Alice Henkeland Hadleigh Marsh, Assistants. 
G. A. Russell, Special Agent. 

2 
235 



LETTER OF TRANSMITTAL. 



U. S. Department of Agriculture, 

Bureau of Plant Industry, 

Office of the Chief, 

Washington, D. C, October I4, 191 L 
Sir : I have the honor to transmit herewith and to recommend for 
puhUcation as Bulletin No. 235 of the series of this Bureau a manu- 
script prepared by Mr. Frank Rabak, Chemical Biologist, entitled 
" Wild Volatile-Oil Plants and Their Economic Importance : I. — Black 
Sage; II. — Wild Sage; III. — Swamp Bay," submitted by Dr. R. H. 
True, Physiologist in Charge of the Office of Drug-Plant, Poisonous- 
Plant, Physiological, and Fermentation Investigations. 

At present the various mdustries making use of volatile oils and 
their derivatives find their supply of these materials m products 
obtained from Old World plants grown in foreign lands. In some 
cases, because of the difficulty m producing these substances, it is 
Hkely that this commercial situation will persist for some time, but 
in other cases it seems likely that American resources may be capable 
of utilization. In our wild flora there are many oil-containing plants 
of considerable commercial promise and the purpose of this bulletin 
is to bring to notice the results of investigations which have been 
carried on with a number of these plants and to point out their com- 
mercial utility. It is presented as the first of a series, to be followed 
from time to time with the results of further investigations which 
are to be carried on with this class of plants and their products. 
Respectfully, 

B. T. Galloway, 

Chief of Bureau. 
Hon. James Wilson, 

Secretary of Agriculture. 

235 Q 



CONTENTS 



Page. 

Distribution of wild aromatic plants 7 

Present production of volatile oils from wild plants native to the United States. . 7 

Classification of volatile oils based on their odors and constituents 8 

Commercial importance of volatile oils and their constituents 8 

Plant sources of camphor, borneol, and cineol (eucalyptol) 10 

Commercial uses of camphor, borneol, and cineol 13 

Purpose of the investigation of wild aromatic plants native to the United States. . 14 

S])ecial investigations 14 

Black sage 14 

Botanical description and distribution 14 

Distillation of the oil I4 

Separation of stearoptene 15 

Identification of camphor I5 

Chemical examination of the oil Ig 

Chemical constants Ig 

Free acids Ig 

Combined acids ig 

Fractionation of the oil I9 

Identification and separation of the constituents 20 

Pinene 20 

Cineol, or eucalyptol 20 

Camphor 20 

Summary 21 

Wild sage 21 

Botanical description and distribution 21 

Distillation of the oil 21 

Separation of stearoptene 23 

Identification of crystalline compound 23 

Chemical examination of the oil 24 

Chemical constants 24 

Free acids 25 

Combined acids 25 

Fractionation of the volatile oil 26 

Identification and separation of the constituents 27 

Cineol 27 

Fenchone 27 

Borneol 28 

Esters of borneol 28 

Summary 28 

Swamp bay 29 

Botanical description and distribution 29 

Distillation of the oil 30 

Chemical examination of the oil 31 

Chemical constants 31 

Free acids 31 

Combined acids 32 

Soluble combined acids 32 

Insoluble combined acids 32 

2--^5 5 



6 ILLUSTRATIONS. 

Special investigations— Continued . 

Swamp bay — Continued. Page. 

Fractionation of the oil and separation of the stearoptene 32 

Identification of the constituents of the oil 34 

Camphor 34 

Aldehyde constituent 34 

Cineol, or eucalyptol 34 

Borneol 35 

Summary 35 

Conclusions 36 



ILLUSTRATIONS 



I 

I 



Page. 

Fig. 1. A plant of black sage {Ramona stachyoides) growing near Riverside, Cal. . 15 

2. Flowering top of a plant of black sage 16 

3. A plant of wild sage {Artemisia frigida) 22 

4. A field of wild sage near Webster, S. Dak 23 

5. A swamp bay tree {Persea pubescens) growing near Orange City, Fla. . . 29 

6. A small branch of swamp bay 30 

235 



B. P. I— 707. 



WILD VOLATILE-OIL PLANTS AND THEIR ECO- 
NOMIC IMPORTANCE: I -BLACK SAGE; II.-WILD 
SAGE; IIL-SWAMP BAY. 



DISTRIBUTION OF WILD AROMATIC PLANTS. 

There exists in the flora of the United States a huge number of 
plant famihes which include species of highly odorous character, 
many of which are known and described botanically as possessing 
pecuhar aromas, but which have received no attention from the 
standpomt of their volatile-oil content. The various sections of 
the country, with their marked difl'erences of soil and cUmate, 
possess floras peculiar to themselves which, if investigated, would 
doubtless reveal many plants valuable for their volatile oils. For 
example, in Florida and the South Atlantic States are found many 
plants with agreeable odors which thrive only in the climate and 
soil of that region. The Central Western States produce numerous 
species of sages and other plants found only in arid and semiarid 
chmates. In the extreme Western States are numerous wild aro- 
matic plants, some of which have been distilled and analyses made of 
the oils obtained therefrom. 

PRESENT PRODUCTION OF VOLATILE OILS FROM WILD PLANTS 
NATIVE TO THE UNITED STATES. 

Only a very few of the wild plants native to this country have 
been distilled and their volatile oils used for commercial purposes. 
Among these may be mentioned longleaf pine, sassafras, wintergreen, 
sweet birch, pennyroyal, horsenunt, and Canada fleabane. 

The first and by far the most important oil distilled from a wild 
plant indigenous to the United States was turpentme oil, which was 
distilled as early as the middle of the eighteenth century. The 
production of this oil is rapidly declinmg, owuig prmcipally to the 
employment of very wasteful methods, which have resulted m the 
destruction of many of the large pme forests. Turpentine is still 
obtained, however, from the longleaf pine {Pinus palustris), which 
occurs quite abundantly in the South Atlantic States from Virginia 
to Florida. The price of this valuable oil has risen so rapidly in 
recent years, owuig to the shortage of raw material from which it is 
distilled, that a suitable substitute would be most desirable. This 



8 WILD VOLATILE-OIL PLANTS. 

problem is now receiving the attention of scientific research workers, 
but no satisfactory substitute which can supply the trade has yet 
been found. 

The commercial distillation of sassafras, wintergreen, and sweet 
birch possibly rank next in importance, although the oils are pro- 
duced on a considerably smaller scale. These oils are used extensively 
by perfumers, confectioners, and manufacturers of toilet soaps. 
The plants are gathered in their native habitats and the quality of 
the oil depends upon the freedom from extraneous material, which 
can be insured only by extreme care in collection. 

The production of pennyroyal and Canada fleabane oils from the 
wild plants is also carried on in a small way. The oils from these 
plants possess valuable therapeutic action and are used principally 
in medicinal preparations. 

Horsemint and wild bergamot are wild aromatic plants which have 
been more recently distilled for their volatile oils. The use of these 
plants was brought about by the discovery that their oils contain, 
respectively, the valuable antiseptics thymol and carvacrol. The 
production of the oils, however, is not being carried on to any great 
extent. 

These few species are practically the only wild aromatic plants of 
the United States which are at present being utilized for their 
volatile oils, and no attempt has yet been made to cultivate them 
in order to improve the quality or to increase the yield of the oils. 

CLASSIFICATION OF VOLATILE OILS BASED ON THEIK ODORS 
AND CONSTITUENTS. 

Volatile oils obtained from plants possess a great variety of odors, 
with no two exactly alike, although many are very closely related. 
A classification of these oils based on their odors is not satisfactory, 
since many which would not be considered as related if judged only 
by the sense of smell have chemical relationships, containing sub- 
stances belonging to the same general class of chemical compounds. 
For our purpose volatile oils are divided into the following classes, 
basing the divisions upon odors and constituents. These groups 
comprise the majority of oils, but they are not arranged in the order 
of their importance : 

(1) CampJioraceous oils, possessing a characteristic camphorlike 
odor, with camphor or camphor-related compounds predominating, 
as in the oils obtained from the camphor tree and from many of the 
sages. The products obtained from camphoraceous oils are exten- 
sively employed in the arts and in medicine. 

(2) Terehinthinate oils, having a characteristic turpentinelike odor. 
These oils are obtained largely from the pine family, the turpentines 
of commerce being examples. They are composed largely of terpene 

235 



COMMEECIAL IMPORTANCE OF VOLATILE OILS. 9 

hydrocarbons and find extensive application in tlie paint and varnish 
industries. 

(3) Sulphur-containing oils, a small group characterized by ex- 
tremely disagreeable and offensive odors, such as those of mustard, 
asafetida, garlic, and onion. These oils contain as their chief con- 
stituents sulphids, sulphocyanates, or nitriles, and are used prin- 
cipally for medicinal purposes. 

(4) Phenol and fhenol-related oils, containing phenols or phenol 
derivatives and characterized by strong, persistent odors, some very 
pungent and others pleasant. Owing to their phenolic constituents 
the density of these oils is usually very high. Common examples 
of this class are the oils of thyme, cloves, cinnamon, sassafras, anise, 
fennel, and the monardas. The usefulness of phenol and phenol- 
related oils depends largely upon their antiseptic properties, the 
principal constituents being thymol, carvacrol, eugenol, anethol, 
chavicol, safrol, and their derivatives. 

(5) Oils containing esters or alcohols, by far the largest group, con- 
sisting of the fragrant oils which are used principally for perfumery 
purposes, although some find a use in medicine. The chief con- 
stituents of these oils are usually alcohols and esters, some few 
containing aldehydes, ketones, oxids, and lactones. Prominent here 
are the alcohols menthol, iinalool, geraniol, citronellol, sabinol and 
their esters, benzyl alcohol and its esters, and anthranilic acid and 
its esters, forming the chief constituents of the oils of peppermint, 
lavender, geranium and rose, citronella, savine, ylang-ylang, and 
orange flowers, respectively. Other constituents are the aldehydes 
citral and citronellal from lemon and lemon-grass oils, and the 
ketones thujone, menthone, pulegone, carvone, and methyl hep- 
tenone from the oils of wormwood, peppermint, pennyroyal, caraway, 
and rue. The oxid cineol from eucalyptus and many other oils, and 
the lactone sedanolid from celery oil are further examples. 

All volatile oils capable of being isolated from wild aromatic plants 
will fall into one or more of the foregoing divisions although, it must 
be understood, the classification is far from being satisfactory. It 
will, however, serve to elucidate the fact that although plant odors 
are of a very variable character they still possess some relationship. 

COMMERCIAL IMPORTANCE OF VOLATILE OILS AND THEIR 

CONSTITUENTS. 

Not only do volatile oils as such find important uses in commerce, 
but the great variety of constituents, one of which in many cases 
forms the major part of an oil, find equally important uses com- 
mercially. 

Such constituents as have antiseptic properties occur widely in 
plant oils and are of untold value to the medical profession, to the 
15520°— Bui. 235—12 2 



10 WILD VOLATILE-OIL PLANTS. 

manufacturer of pharmaceutical preparations, and to the maker of 
toilet lotions and dentifrices. Many volatile oils also contain con- 
stituents which are recognized as very important in the perfumery 
industries, their value depending not so much upon their own inlierent 
odor as upon the effect which they produce in modifying or toning 
the fragrance of a mixture of several components. The finest per- 
fumes are often mixtures of odors blended together and frequently 
contain oils which in themselves would not be regarded as very 
agreeable or pleasing in odor. In some instances a single constituent, 
as for instance citral, the chief constituent of lemon-grass oil, is used 
in its own pure condition without the admixture of other odors, as 
in the scenting of fine toilet soaps. 

As flavoring agents considerable use is made of many of the volatile 
oils or of their constituents. For example, the oils of sassafras, 
peppemiint, cinnamon, and wintergreen are used by confectioners in 
the flavoring of candies. The chief constituents of these oils (safrol, 
menthol, cinnamic aldehyde, and methyl salicylate) can, with the 
exception of menthol, be used with equal efficiency. 

Many essential oils and the compounds isolated from them have 
proven highly useful in therapeutics, and enter into a number of 
medicinal preparations. Such constituents as menthol from pep- 
permint oil, eugenol from clove oil, methyl salicylate from winter- 
green and sweet-birch oils, thymol from thyme and horsemint oils, 
camphor from camphor oil, borneol from Borneo camphor oil, cineol 
from eucalyptus oil, and many others, comprise a group of medica- 
ments which are indispensable. 

From the foregoing account of volatile oils and their important 
constituents may be obsei^ed the possibilities which lie in this field 
of investigation. It is probable that a thoroughgoing examination 
of the wild flora of the United States would reveal the presence of 
volatile oils in many plants which at present are not known to yield 
volatile products. This possibility should stimulate the search for 
these products with a view to their commercial utilization. 

PLANT SOURCES OF CAMPHOR, BORNEOL, AND CINEOL 
(EUCALYPTOL). 

Owing to the presence in large quantities of the compounds cam- 
phor, borneol, and cineol in the oils to be described in this bulletin, 
the usual sources of these compounds are herewith presented, together 
with their commercial uses. 

The occurrence of camphor in the vegetable kingdom as a com- 
ponent of volatile oils has been noted chiefly in such plant families as 
the Lauraceae, Compositse, Labiatse, and Zinziberaceae. The source 
of commercial camphor at present is the camphor tree, Cinnamomum 

235 



PLANT SOURCES OF CAMPHOR, BORNEOL, AND CINEOL. 11 

camphora (Laurus camphora), indigenous to Japan and Formosa. 
This tree has been introduced into the United States and experi- 
ments are now being conducted in Florida for the production of 
camphor, with some degree of success. 

Two modifications of camphor occur in nature, the commercial 
variety, or dextrogyrate (rotating the plane of polarization to the 
right), and the levogyrate (having the opposite rotation). Com- 
paratively few plants native to this country have been found to 
yield camphor. Whittelsey^ has recently succeeded in isolating 
and identifying levo camphor in considerable quantities from the 
oil of a western sagebrush (Artemisia cana Pursh., family Compositse). 
Camphor has been observed in the native plant Sassafras variifolium 
(Sassafras officinalis), a tree belonging to the family Lauraceae. Ac- 
corcUng to Power and Kleber,^ sassafras oil contains from 6 to 8 per 
cent of dextro camphor. Traces of camphor have also been observed 
in tansy oil,^ obtained from Tanacetum vulgare, a plant which is cul- 
tivated in the Eastern States for its volatile oil. 

Borneol, or Borneo camphor, is closely related to camphor and 
possesses very similar properties. It is derived chiefly from the 
Borneo camphor tree (Dryobalanops aromatica (D. camphora), family 
Dipterocarpacese), and is found in crude crystalline condition in the 
natural cavities of the wood.* Blumea halsamifera (family Compositse), 
a shrubby plant ^ native to India, also yields considerable c{uantities 
of borneol," known to the natives as ngai camphor. The presence of 
borneol in plants native to this countiy is restricted to a few species, 
where it appears in the free condition only as a trace, being found 
more widely distributed as esters. It has been found in small 
quantities in the oil of red cedar (Juniperus virginiana) ,'' and in 
thuja oil from the arborvitse (Thuja occidentalis) ,^ both trees being 
found abundantly in various sections of the United States. Small 
quantities have been found in the oils of other native plants, such as 
the goldenrod (Solidago canadensis),^ Virginia snakeroot (Aristolochia 
serpentaria,^^ Texas snakeroot (Aristolochia reticulata) ,^^ Canada 

> Whittelsey, Th. A New Occurrence of l-Camphor. Otto Wallach Festschrift. Gottingen, 1909, 
pp. 6(5S-670. 

« Power, F. 15., and Kleber, C. On the Chemical Composition of the Oil of Sassafras lidrk and Oil of 
Sassafras Leaves. Pharmaceutical Review, vol. 14, 1896, pp. 101-104. 

3 Sehimmel & Co., Semiannual Report, October, 1895, p. 47. 

'* Kremers, E. Borneo Camphor. Pharmaceutical Review, vol. 23, 1905, pp. 7-14. 

^ The earlier name for this genus is Placus (Lourelro, 1790), the name Blumea being published by 
De Candolle in 1833. 

« Sehimmel & Co., Semiannual Report, April, 1895, p. 76. 

'Ibid., 1898, p. 14. 

8 Wallach, O. Untersuchungen aus dem Universitatslaboratorium zu Gottingen, XIV. 4. ITeber das 
Semicarbazon des d- and 1-Fenchons und das Vorkommen von 1-Borneolester im Thujaol. Nachrichten 
der Koniglichen Gesellschaft der Wissenschaften zu Gottingen, vol. 1, 1905, p. 11. 

' Sehimmel & Co., Semiannual Report, April, 1897, p. 46. 

'" Spica, M. Studio Chimico dell' Aristolochia Serpentaria: Nota Preliminare. Gazzetta Chimica 
Italiana, vol. 17, 1887, pp. 313-316. 

" Peacock, J. C. Volatile Oil of Aristolochia Reticulata, Nuttall. American Journal of Pharmacy, 
vol. 63, 1891, pp. 257-264. 

235 



12 WILD VOLATILE-OIL PLANTS. 

snake root (Asarum canadense),^ tansy {Tanacetum vulgare),^ and 
sweet gum (Liquidamhar styracijiua) .'^ As its acetic acid ester, it 
occurs in the oils of a large number of sjjecies of pines and firs. 

Borneol and camphor occur occasionally together in the same oils. 
Their association is not surprising, since the relationship of the two 
compounds is very close. By oxidation borneol is readily converted 
into camphor. The two compounds have been observed together in 
the oil of cardamon,* distilled from the seeds of Amomum carda- 
momum; also in the oil of rosemarj^, from the plant Rosmarinus 
officinalis,^ and in spike oil, obtained from Lavandula spica,^ the 
latter two belonging to the mint family. 

Cineol, or eucalyptol, is found chiefly in the volatile oils from various 
species of the eucalyptus tree and is the principal constituent of many 
of these oils. The blue gum tree {Eucalyptus globulus), belonging to 
the family Myrtacese and introduced abundantly in the western part 
of the United wStates, furnishes a volatile oil of which more than one-half 
is cineol. Other important sources also are cajuput oil^ and niaouli 
oiP from Melaleuca leucadendron {M. viridijlora) , a plant indigenous 
to India. Only a few native aromatic plants are known to yield 
volatile oils which contain cineol and in only a very few cases has 
this constituent been found to be present in any quantity. It is 
known to occur in the oil of the California laurel, or mountain laurel 
(JJmheXlularia calif ornica) ,^ where it is present to the extent of about 
20 per cent. Among other native plants in which cineol is known to 
occur in small quantities is the composite Acliillea millefolium,^'^ com- 
monly known as milfoil or yarrow. Peppermint oil from Mentha 
piperita^'- and sage oil from Salvia officinalis^^ are said to contain small 
quantities of this constituent. 

Camphor, borneol, and cineol are found in considerable quantities 
in volatile oils which have been distilled from three unutilized aro- 
matic plants of the United States, which will be discussed fully in 
the subsequent pages of this bulletin. 

I Power, F. B., and Lees, F. H. The Constituents of the Essential Oil of Asarum Canadense. Journal 
of the Chemical Society, London, vol. 81, 1902, pt. 11, pp. 59-73. 

' Schimmel & Co., Semiannual Report, October, 1895, pp. 46-47. 

sjbid., April,1898, p. 53. 

* Ibid., October, 1897, p. 12. 

6 Gildemeister, E., and Stephan, K. Beitriige zur Kenntniss der iltherisehen Oele, VI. Archiv der 
Pharmazie, vol. 235, 1897, p. 585. 

6 Bouchardat, G. Surl'Essence d' Aspic (Lavandula Spica). Comptes Rendus, Academic des Sciences, 
vol. 117, 1893, pp. 53-56. 

» Wallach,0. tjber die Bestandtheile einiger atherische Oelc. Justus Liebig's Annalen der Chemie, 
vol. 225, 1884, pp. 314-318. 

8 Bertrand, G. Sur la Composition Chimique de I'Essence de Niaouli. Comptes Rendus, Societe des 
Sciences, Paris, vol. 116, 1893, pp. 1070-1073. 

« Power, F. B.,and Lees, F. H. The Constituents of the Essential Oil of California Laurel. Journal of 
the Chemical Society, London, vol. 85, 1904, pt. 1, pp. 629-639. 

10 Schimmel & Co., Semiamiual Report, October, 1894, p. 38. 

II Power, F. B., and Kleber, C. The Constituents of American Peppermint Oil, and a Method for the 
Quantitative Determination of Menthol. Pharmaceutische Rundschau, vol. 12, 1894, pp. 157-165. 

12 Wallach, O. Zur Kenntniss der Terpene und der iitherischen Oele. Justus Liebig's Annalen del 
Chemie, vol. 252, 1889, pp. 94-157. 
235 



COMMERCIAL USES OF CAMPHOR, BORNEOL, AND CINEOL, 13 

COMMERCIAL USES OF CAMPHOR, BORNEOL, AND CINEOL. 

As an article of commerce camphor is most useful, being employed 
extensively in the arts and in medicine. Its use in the arts is restricted 
principally to the manufacture of celluloid, a commodity which finds 
a great variety of uses. It also finds important uses in the manufac- 
ture of lacquers and pyrotechnics, in embalming, and, because of its 
odor, is used as an insectifuge. Camphor is also used to a great 
extent in medicine both for external and internal application, and 
enters into many pharmaceutical preparations. 

Borneol, although closely allied to camphor, is much less used com- 
mercially in the United States, principally because of the difficulties 
encountered iii its collection by the natives in Borneo and the Malay 
Archipelago. It would probably be used more extensively in this 
country if a sufficient supply could be obtained at reasonable prices, 
the high price of the article preventing its use for technical purposes. 

Borneol is antiseptic and stimulant, and finds its main use in 
medicine, but is also in demand in the perfume industry, the esters 
being especially desirable. The acetic acid ester of borneol (bornyl 
acetate) is in fact the odoriferous principle of pine-needle odor. 
Borneol is used mainly as a base for the manufacture of bornyl 
acetate which is much used in the preparation of pine-needle odors 
by perfumers. It is in considerable demand in the Orient where, 
according to Janse,^ it is sought by the Chinese, who use it 
principally in religious ceremonies, but also in medicine and the 
perfuming of India inks. The Chinese are said to pay as much as $1 .25 
an ounce for it, and since the native producers are unable to supply the 
demand, a synthetic borneol, which is not a pure substance but a 
mixture of borneol and isoborneol, has entered the markets of the 
East. 

Cineol, or eucalyptol, is a very important and valuable article of 
commerce. Its virtue as a remedial agent has placed it in a high 
position among the important drugs used in the treatment of human 
ailments. The uses of cineol are entirely medicinal. It is used both 
internally and externally, and also as an inhalant. It is administered 
internally in the form of various pharmaceutical preparations for the 
treatment of colds, pneumonia, bronchitis, and other respiratory 
affections. As an inlialant it is used for asthma, diphtheria, and 
throat troubles in general. Together with other medicaments cineol 
is applied externally in the form of ointments or liniments. Further- 
more, it has a wide application in the manufacture of dentifrices, 
mouth washes, and other preparations where an antiseptic action is 
desired. At the present time pure cineol, as prepared from eucalyp- 
tus oil, commands a price of SI to $2 a pound. 
■ 1 

•Janse, J. M. Le Dryobalanops Aromatica Gaertn. et le Camphre de Borneo. Annales du Jardin 
Botanique de Buitenzorg, supplement 3, pt. 2, 1910, pp. 947-961. 
235 



14 WILD VOLATILE-OIL PLANTS. 

PURPOSE OF THE INVESTIGATION OF WILD AROMATIC PLANTS 
NATIVE TO THE UNITED STATES. 

Since many valuable volatile oils and volatilo-oil constituents have 
been discovered in plants growing wild in various parts of the world, 
it has been thought that an investigation of the wild aromatic plants 
of this country would reveal many, now practically useless and possi- 
bly classed as weeds, which might become of commercial value. 

The economic value of these plants is determined not only by the 
proportion of oil which they contain, but by the constituents of the 
oil; hence careful analyses must be made in order to discover what 
these constituents may be. The present bulletin deals with the 
analyses of three heretofore unutilized plants, which may be grouped 
together, because the oils obtained from them are all of a camphora- 
ceous character and because they contain several constituents in 
common. These, gathered from different sections of the United 
States from entirely different habitats and belonging to unrelated 
families, are as follows: Black sage (Ramona stachyoides) from Cali- 
fornia, wild sage (Artemisia frigid a) from South Dakota, and swamp 
bay (Persea pubescens) from Florida. 

SPECIAL INVESTIGATIONS. 

BLACK SAGE. 

BOTANICAL DESCRIPTION AND DISTRIBUTION. 

Ramona stachyoides (Benth.) Briquet (synonyms — Audihertia stach- 
yoides Benth., Salvia mellifera Greene), commonly known as black 
sage (figs. 1 and 2), is a shrubby aromatic perennial, occurring from 
middle to southern California on low hills from April to June. The 
shrub attains a height of 3 to 6 feet and possesses herbaceous leafy 
branches with oblong leaves, green and wrinkled above and ash 
colored and hairy below The flowers are white or lilac and in whorls 
or heads. The leaves have a strongly aromatic and decidedly cam- 
phoraceous odor, the woody branches being very brittle and also 
strongly aromatic. 

DISTILLATION OF THE OIL. 

A quantity of the fresh herb partly in bloom, including the flowering 
tops, branches, and leaves, was distilled by steam in the vicinity of 
Los Angeles, Cal., in April, 1908, and yielded 0.75 per cent of oil. 
The oil was nearly colorless and possessed a penetrating, camphora- 
ceous, yet agreeable odor, with a bitter, camphorlike taste. At 24° C. 
the specific gravity was found to be 0.9144; specific rotation Ad = 
+ 30.2°; re-fraction at 24° C, 1.4682. The oil was soluble with 
clear solutioa in 1 ^ volumes of 70 per cent alcohol, becoming turbid 
with 3^ volumes or oven 

235 



BLACK SAGE. 



15 



SEPARATION OF STEAROPTENE. 

Owing to the very strong camphoraecous odor of the oil, a se})ara- 
tion of the stearoptene suggested itself. In order to separate a 
soHd body which is held in solution by a volatile oil, the "freezing- 
out" method is usually employed. Accordingly 100 grams of the 
oil were subjected to a freezing mixture of ice and salt. A tem})era- 
ture of — 15° C. was attained, and flaky crystals formed throughout 
the oil. The crystals were separated by being thrown on a force 
filter and the remaining oil again subjected to the cold, when a 
second lot was obtained, which was likewise separated. A total of 




Fig. 1.— A plant of black sage {Ramona stachyoides) growing near Riverside, Cal. 

11.3 grams of crystals was separated, corresponding to a yield of 
11.3 per cent. These crystals were soft and flaky in nature and 
possessed the characteristic odor of camphor. 



IDENTIFICATION OF CAMPHOR. 

In order to identify the crystalline substance obtained from the 
oil, a small quantity was sublimed, and the usual tests of melting 
point, boiling point, and rotation were apphed. For further recog- 
nition of the compound, an attempt was made to prepare an oxime. 
Accordingly the method of Auwers * was applied, which, briefly, is as 

\ Auwers, K. Zur Darstellung der Oxiine. Berichte der Deutsehen Chemischen Oesellsphaff , vol. 22, 
1889, pp. 604-607. 
235 



16 



WILD VOLATILE-OIL PLANTS. 



follows: To a solution of 10 parts of camphor in 10 to 20 times the 
amount of 90 per cent alcohol is added a solution of 7 to 10 parts of 
hydroxylamine hydrochlorid and 12 to 17 parts of a soda solution. 
If turbidity results, more alcohol is added and the mixture is heated 
on a water bath until a small portion of the solution remains clear 
upon the addition of water or until the resulting turbidity disappears, 




Fig. 2.— Flowering top of a plant of black sage. 

when a few drops of soda solution are added and no free camphor 
remains. The mixture is then diluted with water, filtered if neces- 
sary, and neutralized with dilute hydrochloric acid. The camphor 
oxime which separates is recrystallized from alcohol or ligroin. It 
melts at 118° to 119° C. 

The above method applied to the sublimed crystals resulted in 
the formation of an oxime which melted at 120° to 124° C. Since 

235 



BLACK SAGE. 



17 



an oxime was obtained (indicating possible ketonic cbaractersj, 
application was made of another reaction for ketones, namely, the 
formation of semicarbazone. Tiemann's method ^ for the prepara- 
tion of camphor semicarbazone Avas aj)j)lied. The method is as 
follows: 1.5 grams of camphor dissolved in 2 cubic centimeters 
glacial acetic acid are treated with a solution of 1.2 grams of semi- 
carbazid In^drochlorid and 1.5 grams of sodium acetate in 2 cubic 
centimeters of water. Water is added and the crystalline compound 
recrystallized from alcohol. The melting ])oint of camphor semi- 
carbazone is 236° to 238° C. 

The sublimed crystals when treated in tlie above manner yielded a 
semicarbazone which melted at 232° C. 

For a comparison of this substance with pure camphor, a tabula- 
tion was made of the more common j)hysical properties and chemical 
tests. 

Table I. — Coitiparison of properties of crystals from oil of hhtrk sage and of pvre 

aimphor. 



Test. 



I Crystals from oil of black sage. Crystals of pure camphor 



Melting point 

Boiling point 

Rotation in 50 iinn. 

Oxime 



174° to 175° C 

205° C 

+3.33° (20 per cent solution 

in alcohol). 
M. p. 120° to 124° C 



Semicarbazone < M. p. 232° to 233° C. 



175° C. 
204° C. 
+3.51° (20 per cent solution 

in alcohol). 
118° to 119° C. 
236° to 238° C. 



The table shows verv close similarities in the melting point, boiling 
point, and rotation of the crystals from the oil of black sage and of 
pure camphor. The melting points of the oximes and semicarba- 
zones, though not corresponding so well, seemed to indicate that the 
crystals were in all probability camphor. To further confirm the 
assumption that the compound from the oil was camphor, an ele- 
mentarv analysis of the compound was made after being twice 
sublimed. 

0.1273 gram of crystals gave 0.1199 gram ILO, corresponding to 10.5 per cent hy- 
drogen. 
0.1273 gram of crystals gave 0.3228 gram CO.,, corresponding to 79.7 per cent carbon. 
CipHigO . r79 per cent carbon, 

camphor ^ ' llO. 5 per cent hydrogen. 
0.1279 gram of crystals gave 0.1244 gram H2O, corresponding to 10.8 per cent hy- 
drogen. 
0.1279 gram of crystals gave 0.3761 gram CO2, corresponding to 79.9 per cent car- 
bon dioxid. 



1 Miehaelis, A., and Erdmann, G. Ueber die Thioaylaniine der Amidoazoverbindungea und der Naph- 
tylendiamine. Beriehte der Deutschen Chemischea Gesellschaft, vol. 28, 1895, pt. 2, pp. 2192-2204. 



15520°— Bul. 235—12- 



18 WILD VOLATILE-OIL PLANTS. 

The combustion results seemed to indicate that the compound is 
identical with that of camphor, as the above tabulation also clearly 
shows. 

CHEMICAL EXAMINATION OF THE OIL. 

CHEMICAL CONSTANTS. 

Preliminary to the detailed chemical examination of the oil the 
usual chemical constants were determined. 

By neutraHzation of a weighed quantity of the oil with standard 
potassium hydroxid V. S., the acid number (the number of millig'rams 
of potassium hydrate required to neutralize 1 gram of oil) was found 
to be 2. 

The ester number (the number of milligrams of potassium hydroxid 
required to saponify the esters in the oil) was found to be 2.5, which, 
calculated as bornyl acetate, corresponds to 0.88 per cent. 

The ester number after acetylization of the saponified oil \vith 
acetic anhydrid (and which represents the total amount of alcohols 
present) was 27.1, which, calculated as borneol, represents a total of 
7.58 per cent of borneol in the oil, both free and in combination. 

FREE ACIDS. 

The original oil was slighth' acid, as indicated by the acid number 
previously mentioned. The free acid was shaken out from a quantity 
of the oil with a 10 per cent solution of sodium carbonate. The 
shaking was repeated several times and the alkaline liquids united. 
The united alkaline liquids were shaken out with ether in order to 
remove any oil held in suspension. The sodium-carbonate solution 
was then evaporated to a small bulk on a water bath, acidified with 
sulphuric acid, and distilled with steam. No oily globules separated, 
showing absence of higher insoluble acids. The distillate, which was 
decidedly acid, was neutralized with sodium-carbonate solution and 
evaporated to a small volume. The liquid which now represented the 
sodium salts of the free acids present in the oil was precipitated frac- 
tionally with a dilute silver-nitrate solution. Four fractions resulted. 
Each fraction was dried to constant weight and burned. 

Fraction 1. 0.1014 gram silver salt=0.0785 gram silver=76.3 per cent silver. 
Fraction 2. 0.1000 gram silver salt=0.077 gram silver=77 per cent silver. 
Fraction 3. 0.1116 gram silver &alt=0.0859 gram silver=76.9 per cent silver. 
Fraction 4. 0.1088 gram silver salt=0.077 gram silver=70.8 per cent silver. 

Fraction 4 indicates the presence of formic acid, the silver salt of 
which requires, theoretically, 70.5 per cent of silver. Fractions 1, 2, 
and 3 indicate silver carbonate (which requires, theoretically, 78 per 
cent of silver) with a slight admixture of silver formate. The 
presence of silver carbonate was caused by a possible slight excess 
of sodium carbonate being added when the acid distillate was neu- 
tralized. 

235 



BLACK SAGE. 19 



COMBINED ACIDS. 



Saponification. — For the purpose of determining the acids held in 
combination in the oil in the form of esters, the oil was saponified 
with alcoholic potassium hydrate by heating on a water bath with 
a reflux condenser for one-half hour. Water was added to the 
mixture, and the oil separated in a layer. After removing the excess 
alcohol on a water bath, the alkaline solution was sliaken out with 
ether to remove any adhering oil. The remaining solution was 
evaporated to a small volume, acidified with sulphuric acid, and 
distilled with steam. 

The distillate from the above was extracted with ether and the 
ether evaporated spontaneously. Only a trace of an acid residue 
remained, which was neutralized with a solution of potassium 
hydroxid and precipitated in three fractions: 

Fraction 1. 0.1012 gram silver !salt=0.0893 gram silver=88 per cent silver. 
Fraction 2. 0.0774 gram silver salt=0.0637 gram silver=82.3 per cent silver. 
Fraction 3. 0.0758 gram silver salt=0.0502 gram silver=66.2 per cent silver. 

The first two precipitates, when dried, consisted principalh' of 
silver oxid, which, theoretically, contains 89.2 per cent of silver. A 
slight excess of potassium hydroxid during neutralization was 
doubtless responsible. Fraction 3 would seem to point to the pres- 
ence of acetic acid in the oil, silver acetate requiring 64.6 per cent of 
silver. 

The aqueous acid portion remaining after the ether extraction was 
neutralized with sodium carbonate concentrated to small bulk and 
precipitated with silver nitrate in three fractions. Fraction 1 con- 
tained 76.2 per cent of silver; fraction 2, 77 per cent; and fraction 3, 
74 per cent. Since silver formate contains 70.5 per cent of silver, a 
trace of formic acid is possibly present in the oil in combination. 

The esters of the oil, as shown by the above results, are present in 
the oil principally as acetates, with a possible trace of formates. 

FRACTIONATION OF THE OIL. 

In order to ascertain tlie total percentage of camphor and to 
separate the remaining constituents as completely as possible, a 
quantity of the oil was fractionated into seven fractions, as follows: 

Fraction 1, 160° C; fraction 2, 160° to 170° C; fraction 3, 170° to 
178° C; fraction 4, 178° to 182° C; fraction 5, 182° to 186° C; 
fraction 6, 186° to 190° C; fraction 7, 190° to 195° C. These frac- 
tions (125 grams) were refractionated into 10 se])arate fractions, as 
shown in Table II, a determination of the physical properties of each 
fraction also being made. 

235 



20 



WILD VOLATILE-OTL PLAXTS. 



Table II. — Fractionation of the oil 6/ black sage, shoiriucj the j/hi/sical properties of the 

i fractions. 




Fnu'tion. 



Temperature. 



Dis- 
tilled 
over'. 



Rotation 


Re-frac- 


in 50 mm. 


tion 


tube. 


Nj, 28° C. 


Degrees. 




+ 6.9 


1.4570 


+10.1 


1.4613 


+10.1 


1.4640 


+ 10 


1.4648 


+ 10.2 


1.4652 


+ 11.5 


1.4659 


+ 11.1 


1.467.3 


+ 11.7 


1.4683 


+ 11.6 


1.4710 


+ 10.4 


1.4710 




1.4854 





Remarlcs. 



1 

2 

3 

4 

5 

6 

7 

8 

9 

10 

Residue 



Degrees C. 

Below 160 

160 to 170 

170 to 174 

174 to 178 

178 to 182 

182 to 186 

186 to 190 

190 to 195 

195 to 200 

200 to 208 

208 and above 



Per cent. 
2.0 
6.8 
7.8 

12.1 

14.8 
8.6 
8 

8.1 
7. 7 

11.6 

12 



0.8070 
.8768 
.8865 
.8920 
.8996 

..9077 
. 9105 
.9130 
.9170 
.9220 
.9236 



Slight terebinthine odor. 
Cineol-like odor. 

Do. 
Decidedly cineol-like odor. 

Do. 
Slight camphoraoeous odor. 
Strong camphoraoeous odor. 

Do. 

Do. 

Do. 

Do. 



IDENTIFICATION AND SEPARATION OF THE CONSTITUENTS. 

Plnene. — The liist fraction distillinsj below 160° C, and which pos- 
sessed an odor of turpentine, was tested for pinene by means of the 
nitrochlorid reaction.^ A deep blue coloration was obtained with 
slight turbidity, indicating a possible trace of pinene. 

Cineol, or eucalyptol. — Tests were made in fractions 2, 3, 4, 5, and 6 
for cineol, which was easily recognized by its odor. For a qualitative 
test the iodol reaction was used, crystals of cineol iodol which melted 
at 111° to 112° V. forming in each fraction. Fractions 3, 4, and 5, 
which smelled strongly of cineol and which doubtless contained the 
major portion of cineol in the oil, were assayed by means of the phos- 
phoric acid method, as directed in the United States Pharmacopoeia 
for 1900.- From these four fractions a total amount of 22.5 per cent 
of cineol was obtained, calculated from tlie original oil. This figure 
represents approximately the percentage of cineol in the oil, although 
it is low rather than high, since fractions 2 and 6 both showed the 
presence of cineol by qualitative tests, but the quantitative estima- 
tion in these fractions was impossible owing to the preponderance of 
other constituents in the fractions. 

A test for terpinene in fraction 6, by means of the terpuiene nitro- 
site reaction, produced a characteristic blue coloration, but the 
crystalline nitrosite would not separate. 

CampJhor. — A strong odor of camphor being distinguishable in frac- 
tions 7, 8, 9, 10, and in residue, a quantitative separation was made as 
completely as possible by means of the "freezing-out" method. 
Between 186° and 190° C. some crystals of camphor began to form 
m the inner tube of the condenser, and at 195° C. the condenser had 
to be kept jacketed with steam to prevent clogging, so rapidly did the 
camphor distill over. The fractions above 195° C. were practically 

1 Wallach, O. Zur Kenntniss der Terpene. Justus Liebig's Annalen der Cheraie, vol. 245, 1888, p. 251. 

2 Phannacopiria of the United States, 8th decennial revision, 1900, p. 313. 

235 



WILD SAGE. 21 

solid. The camphor which scj)iiiiitc(l at onhiiaiy temperature was 
filtered on a force hlter, and the liquid portion of the fractions sub- 
jected to freezing successively until camplior no longer separated. 
It is apparent that the separation of the camphor from these small 
fractions by freezing out is rather inaccurate because of the losses in 
transferring and fdtering. From the above fractions, however, a 
quantity of camphor was obtamed corresponding to about 40 per 
cent of the original oil. .This figure is low, for the separation on a 
larger scale working with much larger fractions would reduce to a 
considerable degree the loss of camphor which is unavoidable in such 
small fractions. 

The fractions distilling between 195° and 20S° C. yiehled crystals 
when treated with bromin in a petroleum-ether solution of the oil. 
The crystals melted at 130° (". Thujone tribromid melts at 122° ^. 
A trace of thujone is therefore probably present in the oil. It is very 
possible, in view of the fact that the acetylization of the oil disclosed 
some free alcohol, that the last fraction contained some borneol, 
which boils at 212° C. 

SUMMARY. 

The results of the experiments would seem to indicate that the oil 
of black sage is composed essentially of camphor (more than 40 per 
cent) and cineol (22.5 per cent), with a small quantity of an alcohol, 
probably borneol, both free and as an ester, and a small quantity of the 
ketone thujone, with traces of the terpenes pinene and terpinene. Free 
formic acid was found, and only traces of combined acetic and formic 
acids in the form of esters. , 

The constituents of possible economic importance in the oil are 
camphor and cineol, both of which possess considerable medicinal 
value, the former being used also very extensively in the arts. These 
constituents, possessing strong antiseptic virtues, no doubt impart 
antiseptic properties to the oil. Inasmuch as the ^deld of oil from 
the fresh herb approximates 1 per cent, if distilled during the full 
flowering stage, and furthermore, since the plant thrives on low sandy 
hills or wastes, it is very probable that the shrub could be grown 
profitably both for its oil and for the large amount of camphor and 
cineol ca})able of being isolated from it. 

WILD SAGE. 

BOTANICAL DESCRIPTION AND DISTRIBUTION. 

Artemisia frigida WiUd., commonly known as wild sage, mountain 
sage, j)asture sagebrush, and wormwood sage (figs. 3 and 4), is a hardy 
perennial 6 to 20 inches high, with a wood}' base and white silky 



22 



WILD VOLATILE-OTL PLANTS. 



leaves. The numerous yellow flowers, arranged in a racemelike head, 
possess a strongly caniphoraceous odor. The leaves are also strongly 
aromatic. The plant abounds on dry sandy hilltops from the Dako- 
tas west to Idaho, north into Canada, and as far south as Texas. 




Fig. 3.— a plant of wild sage {Arteinisia frigida) . 



DISTILLATIf)X OF THE OIL. 

The oil distilled from wild sage was briefly reported by the writer 
in 1905^ and 1906.^ The promising preliminary results encouraged 
a further investigation of this plant. During the summers of 1907 
and 1908 larger quantities of this interesting wild plant were distilled 

1 Rabak, Frank. On Several New Artemisia Oils. Pharmaceutical Review, vol. 2.3, 1905, pp. 12S-129. 

2 Ibid., vol. 24, igOf), pp. 324-325. 

2:55 



WILD SAGE. 



23 



in South Dakota, ayicldof 0.26 pcicciitof a very fragrant essential oil 
beiiis: obtained from j)lants wliicli had ])assed their flowering stage. 
WHien the plant is distilled during its flowering stage the yield of oil 
is about 0.41 per cent. 

The oil obtained by the distillation of the whole plant was beau- 
tiful ]>ale green in color, with an agreeable fatty and camphoraceous 
odor and a slightly bitter camphorlike taste. The specific gravity 
of the oil at 24° was 0.940; specific rotation Ad= -24.2°; re-frac- 
tion Nd24°, 1.4716. The oil w^as soluble in 1 volume of 80 per cent 
alcohol, becoming turbid in 2 volumes or over. 



&r^ 



■Wr 



**^^a5 





Fig. 4.— a field of wild sage near Webster, S. Dak. 



SEPARATION OF STEAROPTENE. 



Durmg the distillation and filtration of the oil, small crystals were 
observed at the mouth of the distillation apparatus and also at the 
mouth of the funnel after standing over night. In order to separate 
this stearoptene (solid portion of the oil) from the elaoptene (liquid 
portion) 50 grams of the oil were subjected to a freezing mixture of 
ice and salt for several hours. As a result crystals separated in the 
form of white flakes. The crystals were thrown into a force filter 
and weighed, a total of o ])er cent resulting. 



IDENTIFICATIOX OF CRYSTALLINE COMPOUND. 

After recrystallization of the above crystals from alcohol the prop- 
erties of the crystals compared veiy favorably with levo borneol, as 
shown in Table III. 



24 WILD VOLATTLE-OIL PLANTS. 

Table III. — Comparison of properties of crystals from oil of irild sage and of pure 

borneol. 



Test. I Crystals from oil of wild sase. 



Crystals of pure borneol. 



Color 

Odor 

Taste 

Boiling point 

Melting point . . . 
Specific rotation . 



White 

Camphorlike 

Bitter, camphorlike . 

210°to215°C 

203° C 

-32° 



White. 

Camphorlike. 

Bitter, camphorlike. 

212° C. 

203° to 204° C. 

-37°. 



To further confirm the above resuhs, wliich seemed to indicate that 
the compound was identical with levo borneol, an elementary analysis 
was made. 

0.1237 gram of the substance gave 0.3499 gram COo, corresponding to 77.2 per cent 

carbon. 
0.1237 gram of the substance gave 0.1252 gram ILO, corresponding to 11.4 per cent 

hydrogen. 

C.oH.sO requires/"-^ P^*" ^^"^ carbon. 



borneol 1 11. 7 per ,e,ent hydrogen. 

The elementary composition substantiates the assumption that the 
crystals are identical with levo borneol. 

CHEMICAL EXAMIXATION OF THE OIL. 

CHEMICAL CONSTANTS. 

The usual chemical constants were determined, namely, the acid 
number, ester number, saponification number, and acetylization 
number. 

The acid number, denoting the amount .of free acids contained in 
the oil and expressed in milligrams of potassium hydroxid, was deter- 
minetl by simple neutralization of the oil wdth standard potassium 
hydrate volumetric solution. 

The ester number, denoting the amount of esters (combination of 
alcohols and acids) in the oil and expressed in milligrams of potas- 
sium hydroxid, was determined b}^ saponification of the ester com- 
pounds with alcoholic potassium hydrate. 

The acetylization number, or the ester number determinetl after 
acetylization of the oil wdth acetic anhydrid, signifies the total amount 
of alcohol or alcohols in the oil. 

The constants of the oil were determined with the following results : 

Acid number, 2.5, calculated as acetic acid, indicates 0.26 per cent acetic acid. 

Ester number, 25, calculated as bornyl acetate, indicates 8.7 per cent bornyl ace- 
tate, which is equivalent to 6.8 per cent of free borneol. 

Saponification number, 27.5. 

Acetylization number, 139, corresponds to 42.67 per cent of total borneol in the oil, 
or, deducting the 6.8 per cent of free borneol as the ester, to 38 per cent of free borneol. 
235 



WILD SAGE. 25 

Assuming that the stearoptene obtained was borneol, a determina- 
tion of the constants of the stearopteneless oil was made. The acid 
number remained practically the same, being 2.3; the ester number 
differed only very slightly, being 24.7; but the acetylization value 
obtained was. only 132, which corresponded to but 40 per cent of total 
borneol. This is in strict conformity with the assumption, whicli 
seemed to be sufliciently proved, that tlie stearoptene separated from 
the oil by freezing was borneol. The stearopteneless oil was nearly 
3 per cent poorer in borneol than the original oil, as shown above. It 
is to be remembered that 3 per cent of crystalline borneol was removed 
by freezing the original oil, hence the lowering of the borneol content 
of the stearopteneless oil. 

FREE ACIDS. 

The determination of the free acids was accomplished by repeatedly 
shaking a portion of the original oil with a 10 per cent sodium carbon- 
ate solution. After removing the adhering oil from the alkaline 
liquid by shaking with ether, the solution was acidified and distilled 
with a current of steam. A few oily globules floated on the surface 
of the liquid. These were extracted with ether and the ether evapo- 
rated. A small amount of oily residue remained, which was distinctly 
acid. The oily residue was exactly neutralized with sodium hydrate 
and precipitated with sUver nitrate solution in three fractions: 

Fraction 1. 0.0377 gram silver salt gave 0.0162 gram silver=42.9 per cent silver. 
Fraction 2. 0.0206 gram silver salt gave .0.0091 gram'silver=44.1 per cent silver. 
Fraction 3. 0.0663 gram silver salt gave 0.3000 gram silver=45.2 per cent silver. 

The three fractions appear to be a mixture of caprylic and oenan- 
thylic acids. Silver caprylate requires 42.9 per cent silver; silver 
cenanthylate requires 45.5 per cent silver. 

A small amount of the insoluble free acids was therefore caprylic 
acid (octoic acid), the major portion being oenanthylic acid (heptoic 
acid). 

The distillate from wliich the oily acids were extracted by ether 
was still slightly acid and was accordingly neutralized with sodium 
carbonate and precipitated with silver nitrate, two fractions being 
obtained. The first corresponded to silver carbonate, due to a slight 
excess of sodium carbonate; the second, only trifling in quantity, 
indicated the presence of only a trace of formic acid in the free 
condition. 

ffinanthylic, or heptoic, acid seems to be the predominatmg free 
acid in the oil, with slight traces of formic and caprylic, or octoic, 
acids. 

235 



26 WILD VOLATILE-OIL PLANTS. 

COMBINED ACIDS. 

The esters in the oil, being combinations of alcohols and acids, 
serve as a basis for the identification of the acids in combination. 
In order to accomplish a separation of the combined acids a small 
quantity of the oil was saponified with alcoholic potassium hydroxid 
by heating on a water bath for half an hour. After dilution of the 
mixture with water and separation of the oil the alkaline liquid, 
which contained a small amount of the oil held in suspension, was 
shaken out with ether. The liquid was then acidified with sul- 
phuric acid and distilled with steam. The oily globules which sepa- 
rated on the distillate were extracted with ether and the solvent 
evaporated. A small amount of an oily liquid with very offensive 
odor remained. This mixture of' oily acids was neutralized with 
sodium hydrate and precipitated with a dilute solution of silver 
nitrate. Two fractions resulted: 

Fraction 1. 0.0430 gram silver salt gave 0.0160 gram silver=37.2 per cent silver. 
Fraction 2. 0.0440 gram silver salt gave 0.0197 gram silver=44.7 per cent silver. 

From the results obtained it is evident that the fractions consist of 
the silver salt of undecylic acid, which requires theoretically 36.8 
per cent of silver, and silver salt of heptoic (oenanthylic) acid, which 
requires 45.5 per cent of silver. 

The aqueous distillate from the above, after being made neutral 
with sodium carbonate, w^as evaporated to small volume and pre- 
cipitated in three fractions with silver nitrate : 

Fraction 1. 0.243 gram silver salt gave 0.1837 gram silver=75 per cent silver. 
Fraction 2. 0.3255 gram silver salt gave 0.2370 gram 8ilver=72.9 per cent silver. 
Fraction 3. 0.3492 gram silver salt gave 0.1840 gram silver=52.9 per cent silver. 

The greater portion of the soluble combined acids consisted of 
valerianic acid, the silver salt requiring 51.6 per cent of silver. A 
trace of formic acid was also indicated in combination as an ester in 
fraction 2, above. 

The chief acids in combination as esters in the oil appear to be 
oenanthylic (heptoic) and valerianic, the former being preponderant. 
Formic and undecylic acids occur only as traces. All of the above 
are no doubt combined in the oil as esters of borneol. 

FRACTIONATION OF THE VOLATILE OIL. 

One hundred grams of the original oil were subjected to fractionation 
and separated into six fractions of 5 degrees each, beginning with 
175° C. These fractions together with the residue were again frac- 
tionated in order to insure a better separation of the constituents. 

235 



WILD SAGE. 



27 



Table I X . — Fractionalion of oil of wild sage, showing the physical and chemical properties 

of the fractions . 







Specific 


Rotation 


Kster 
number. 


Temperature. 


Distilled. 


gravity 
at 24° C. 


in 50 mm. 
tube. 


Degrees C. 


Per cent. 




Degrees. 




Below 1751 


13. (i 


0. 9084 


- 9.5 


2.6 


175 to 180 


14.0 


.9190 


- 8.1 


6.7 


180 to 185 


6.0 


.9269 


- 7.6 


8.9 


185tol90 


4.5 


.9313 


- 6.4 


12.0 


190 to 195 


10.0 


.9401 


- 8.6 


25.8 


195 to 205 


9.5 


.9478 


- 9.7 


34.8 


205 to 215 


9.0 


.9562 


-10.6 


56.4 


215 to 230 


9.5 


.9600 


-10.8 


75.2 


230 to 245 


3.5 


.9570 


- 5.8 


70.7 


245 and above. 


9.0 


.9830 




47.0 







Remarks. 



1. 
2. 
3. 
4. 
5. 
6. 

7. 
8. 
9. 
10 



Eucalyptuslike (nineol) odor. 
Do. 
Do. 

Slightly eamphoraceous odor. 

Camphoraceous odor. 

Decidedly camphoraceous; free 
borneol crystallized in con- 
denser. 

Fraction almost solid (borneol). 

Fraction partially solidified. 

Few crystals separated. 

Dark, sirupy, camphoraceous. 



1 This fraction distilled largely between 170° and 175° C. 
IDENTIFICATION AND SEPARATION OF THE CONSTITUENTS. 

Cineol. — Fraction 1, 175°C, possessed a strong eucalyptuslike odor 
and was tested for cineol by means of iodol. The tetraiodopyrol 
(iodol) addition product of cineol formed into well-defined, nearly 
colorless crystals, melting at 110° to 113° C. This ciystalline addi- 
tion product of iodol formed in the first four fractions; in fraction 5, 
however, only a trace of crystals appeared. 

The presence of cineol having been proved, a quantitative estima- 
tion of the compound was made in fractions 1, 2, 3, and 4. Fraction 
5, which contained only a very small quantity of cineol, did not admit 
of estimation by the phosphoric-acid method, which is reliable only 
when large percentages of cineol are present. 

The fractions yielded the following percentages of cineol: 1, 40 per 
cent; 2, 70 per cent; 3 and 4, 43.7 per cent. Calculating from the 
original oil as a basis, the above results correspond to 19.7 per cent 
of cineol in the original oil. 

FencJione. — Fraction 5, boiling from 190° to 195° C, was a heavy 
liquid with a strong camphorlike odor. Pure levo fenchone^ from 
thuja oil is an oily liquid with a strong camphoraceous odor; boiling 
at 192° to 194° C; specific gravity at 19° C, 0.946; (Ad)-66.9°. 

An oxime was prepared from the fraction by reaction with hydroxyl- 
amine hydrochlorid according to the method of Wallach,^ which is 
as follows : To 5 grams of f enchone dissolved in 80 cubic centimeters 
of absolute alcohol is added a solution of 1 1 grams of hydroxylamine 
hydroclilorid in 1 1 grams of hot water. Six grams of powdered potash 
are added. The oxime separates in the form of crystals, upon stand- 
ing for some time. Recrystallized from alcohol it melts at 164° to 
165° C. 



I Wallach, O. Zur Kenntniss der Terpene und der iltherischen Oele. 
Chemie, vol. 272, 1892, p. 102. 
Ibid., p. 104. 
235 



Justus Liebig's Annalen der 



28 WILD VOLATTLE-OTL PLANTS. 

The oxime formed from the fraction by the above method, after 
recrystalhzation from ethyl acetate, melted at 170° C. 

Provided that fraction 190° to 195° C. consists chiefly of fenchone 
the oil should contain 8 to 10 per cent of this compound. 

Borneol. — The total amount of borneol contained in the oil was 
determined by the saponification of a small quantity of the original 
oil and subsequently fractionating the saponified oil. Twenty-five 
grams of the saponified oil were carefully fractionated and then re- 
frigerated, 7.5 grams of borneol separating out. This corresponds to 
a total of 30 per cent borneol. After the separation of the borneol 
the oil was again fractionated, and the portion above 195° C. yielded, 
when frozen, an additional 2 grams of borneol, making a total of 9.5 
grams, or 38 per cent, of total borneol separated from the oil. The 
theoretical quantity of borneol in the oil, as shown by the acetyliza- 
tion value, is about 43 per cent, the lower percentage which was 
actually obtained being caused by incomplete separation due to the 
smallness of the amount saponified. 

Esters of horneol. — A careful examination oi Table IV shows that 
the esters of borneol, possibly chiefly bornylheptoate and valerianate, 
are found in the fractions boiling above 190° C, principally in the 
highest boiling fractions; a perfect separation of these esters was not 
feasible because of the existence of the esters as mixtures of several 
acids. The ester numbers of the fractions, however, show the distri- 
bution of the esters at the different temperatures. 

SUMMARY. 

Briefly summarizing the results of the analyses, the oil of wild sage 
may be said to be composed: (1) Of total borneol camphor, 43 per 
cent, of which about 6.8 per cent exists as bornyl heptoate (calculating 
the esters of the oil as heptoic acid salts of borneol), leaving 35.8 
per cent of free borneol camphor present in the oil; (2) of cineol 
(eucalyptol) , 18 to 20 per cent; (3) of fenchone, 8 to 10 per cent; (4) 
of free acids, chiefly oenanthylic, or heptoic, acid, 0.58 per cent, with 
traces of formic and caprylic acids ; (5) of combined acids in form of 
esters, chiefly, oenanthylic acid, with smaller quantities of valerianic, 
undecylic, and formic acids. It is very probable that a small 
amount of terpenes were also present in the portion distilled below 
175° C, wliich, however, were not identified. 

As will be noted from the above, the chief constituents of the oil of 
wild sage are borneol camphor and cineol, each of which possesses 
valuable antiseptic qualities. Since there is a high percentage of 
these constituents, the oil from this wild plant should prove of value 
for medicinal purposes. Another important use of the oil is suggested 
by the high content of borneol, a constituent which finds application 

235 



SWAMP BAY, 



29 



in celluloid manufacture, and which is readily separated from this oil. 
Lastly, combining the agreeable aromatic quality with its antiseptic 
qualities, the oil should prove important as an ingredient of medicinal 
soaps or as a scenting substance. 














Fig. 5.— a swamp bay tree (Persea pubescens) growing near Orange City, Fla. 

Inasmuch as the wild sage plant grows chiefly on sandy and stony 
hills which are practically waste lands and which require but little 
moisture, it would seem that the plant could be cultivated in various 
sections of the Northwestern States. 



SWAMP BAY. 

BOTANICAL DESCRIPTION AND DISTRIBUTION. 

Persea puhescens (Pursh.) Sarg., commonly known as swamp red 
bay or swamp bay (figs. 5 and 6), is an aromatic evergreen tree attain- 
ing a height of 30 feet or more, but usually occurring as a shrub. 
The leaves and twigs of the tree possess a pleasant camphoraceous 



30 



WILD VOLATILE-OIL PLANTS. 



odor. The swamp bay occurs abundantly in swam])s and hammocks 
from North Carohna to Florida and Texas. The tree is a member 
of the family Lauracese, to which the camphor tree belongs. 



DISTILLATION OF THE OIL. 



Because of the strong camphoraceous odor and its close relationship 
to the camphor tree, the extraction and possible utilization of the oil 
from this wild aromatic plant suggested itself. Accordingly, during 
the summer of 1910, with the assistance of !Mr. S. C. Hood, in charge 




Fig. G. — A small branch of swamp bay. 

of the station at Orange City, Fla., a small quantity of the leaves and 
twigs of this plant was distilled and a yield of about 0.2 per cent of 
oil was obtained. But with proper conditions and precautions the 
yield could no doubt be very materially increased, depending largely 
upon the time at which the distillation is made, and also upon the 
proportion of twigs and branches included. The above distillation 
was made late in the summer, long after the blossoming period, the 
stage at which a plant is usually most productive in volatile oils, and 
the material also contained many branches and much woody matter. 



SWAMP BAY. 31 

The oil obtained was pale yellowish brown in color, with a strongly 
aromatic and camphoraceous odor, and a persistent bitter, slightly 
pungent, and camphorlike taste. The specific gravity at 25° C. was 
0.9272; specific rotation, Ad=+22.4°; refraction, N^ 25°= 1.4695. 
The oil was soluble in one-third its volume of 80 per cent alcohol, 
becoming faintly turbid upon the addition of five volumes or more 
of alcohol. 

CHEMICAL EXAMINATION OF THE OIL. 

CHEMICAL CONSTANTS. 

A preliminary examination of the oil disclosed considerable free 
acidit}^, the acid number being 2.8, while the ester content was rather 
low, the ester number being 14.5. The low ester number would seem 
to mdicate a low percentage of alcoholic compounds in combmation 
with acids, and would correspond to 4.9 per cent of esters calculated 
as the acetate of borneol. After acetylization of the oil with acetic 
anhydrid the saponification number was found to be 64, which corre- 
si:)onds to 14.6 per cent of free alcohol, calculated as borneol. 

In order to identify conclusively the constituents of the oil and the 
forms in which they occur, and to separate quantitatively the pre- 
dominant constituents, the oil was subjected to a more careful and 
detailed analysis. 

FREE ACIDS. 

The free acidity of the oil as indicated by the preliminary tests was 
removed by shaking with 10 per cent aqueous sodium carbonate 
solution in several, portions. The aqueous alkalme extracts, after 
being deprived of any adhering oil by extraction with ether, were 
concentrated, acidified, and distilled with a current of steam. The 
acids which were obtamed separatetl prmcipally as oily globules on 
the aqueous distillate, which was only faintly acid. 

The free insoluble acids which were separated from the aqueous 
distillate by extraction with ether and evaporation of the solvent 
were neutralized with a solution of potassium hydroxitl and then 
precipitated in fractions with a solution of silver nitrate. 

Fraction 1. 0.0227 gram silver salt gave 0.0130 gram silver=57.2 per cent silver. 
Fraction 2. 0.0213 gram silver salt gave 0.0119 gram silver=55.8 per cent silver. 

It appears from the above results that the only acid existing in 
the free state in the oil is butyric acid, since silver butyrate gives 
theoretically 55.3 per cent of silver, fraction 1 being slightly con- 
taminated, due possibly to a slight excess of potassium hydrate which 
was added when the acids were neutralized and which would appear 
in the first precipitate. 

From the remainmg faintly acid distillate, after neutralization with 
barium carbonate and concentrating, only a trace of precipitate, 

235 



32 WILD VOLATILE-OIL PLANTS. 

insufficient for silver determination, resulted upon the addition of 
silver nitrate solution. The butyric acid detected in the free insoluble 
acids was evidently extracted by the ether, in which it is very soluble. 

COMBINED ACIDS. 

As stated previously, the oil was found to contam a small percent- 
age of esters, or organic acids in combination with liigher alcohols. In 
order to identify these acids, which are in combination in the form of 
esters, a quantity of the oil, after removmg the free acids, was saponi- 
fied by heatmg on a water bath for half an hour with a slight excess 
of alcoholic potassium hydroxid. The mixture, after saponification, 
was diluted with water and the unsaponified oil separated. The 
alkaline liquid, which now contained the combined acids as their 
potassium salts, after bemg freed from adhermg particles of oil by 
shaking with ether, was acidified with sulphuric acid and distilled 
with steam. The insoluble oily acids which formed on the distillate 
were separated by shaking the distillate lightly with ether and evapor- 
ating the ether. 

SOLUBLE COMBINED ACIDS. 

The aqueous portion of the distillate which contained the soluble 
combined acids of the oil was neutralized with barium carbonate, 
concentrated and precipitated with silver nitrate solution. Only a 
small precipitate resulted. This precipitate was found to contain 
55.9 per cent of silver, which corresponds to silver butyrate. Hence 
the acid in the distillate was butyric acid. 

INSOLUBLE COMBINED ACIDS. 

As heretofore stated, the insoluble oily acids obtained by extrac- 
tion with ether were carefully neutralized with potassium hydroxid 
solution and precipitated fractionally with silver nitrate. Two 
precipitates were obtained which were thoroughly washed and dried. 
The first and largest precipitate assayed 51.2 per cent silver, the 
second assaying 45.1 per cent silver. This would indicate that the 
insoluble acids were valerianic acid (silver valerianate requiring 51.6 
per cent silver), and heptoic acid (silver heptoate requiring 45.5 per 
cent silver), the valerianic acid predominating. 

The results show that the esters of this oil exist as the salts of 
butyric, valerianic, and heptoic acids, valerianic acid esters, however, 
predominating. 

FRACTIONATION OF THE OIL AND SEPARATION OF THE STEAROPTENE. 

For the purpose of accomplishing a separation of the constituents, 
50 grams of the oil, after saponification, were dried and subjected to 
fractional distillation in a three-bulb Ladenburg flask. The results 
are given in Table V. 

235 



SWAMP BAY, 33 

Table V. — Fractionation of saponified oil of swamp bay and description of fractions. 



Frac- 
tion. 



Temperature. 


Distilled. 


Degrees C. 
Below 170 


Per cent. 
1.1 


170 to 182 

182 to 185 

185 to 190 

190 to 195 

195 to 200 


8.8 
9.2 
1.3. 5 
13.0 
5.8 


200 to 205 


12. 5 


205 to 215 


14.0 


215 to 225. 


12. 5 


225 and above. 


9.0 



Remarks. 



Penetrating odor; largest portion of the fraction distilled over below 
80" C; temperature rose rapidly to 170° C. 

Camphoraeeous ciiieol-lilce odor; largest portion distilled 175° to 180°. 

Strong cineol-like odor; temperature ro.se uniformly. 

Cineol-like camphoraeeous odor; temperature roseimiformly. 

Strong camphoraeeous odor; temperature rose uniformly. 

Strong camphorlike odor; crvstals appeared in condenser; ' largest 
portion distilled between 198° to 200° C. 

Strong camphorlike odor; fraction semisolid upon cooling; tempera- 
ture rose uniformly. 

Strong camphorlike odor; fraction almost solid upon cooling; dis- 
tilled largely between 205° to 210° C. 

Strong camphoraeeous odor; fraction semisolid; temperature rose 
uniformly. 

Heavy yellow oil with camphoraeeous odor. 



1 To prevent clogging of the condenser with crystals, the jacket of the condenser was deprived of the cold 
water, and steam passed through, the melted crystals passing over. The crystals immediately reappeared 
in the fractions upon cooling. 

Beginning with fraction 6 each successive fraction was refrigerated 
in a freezing mixture of ice and salt and the crystals separated by 
centrifuging in a platinum Gooch crucible. A total of 13.7 per cent 
of crystals was obtained. 

In order to obtain a further separation of crystals the portions of 
the oil beginning with fraction 5 were fractionated into the following 
fractions: 190° to 195° C; 195° to 200° C; 200° 205° C; 205° to 
215° C; 215° to 233° C; 233° to 260° C. A total of 4 per cent of 
crystals was obtained by refrigeration and centrifugation of those 
fractions in which crystals appeared. The portion between 190° 
and 215° C, and also fraction 4 of the original, were further fraction- 
ated into four parts: 185° to 190° C; 190° to 195° C; 195° to 205° 
C; 205° to 215° C, an additional yield of 3.3 per cent of crystals 
being obtained. 

By the above method of successive fractionation and refrigeration 
a total of 21 per cent of crystals was obtained from the oil. This 
represents only approximately the total percentage of stearoptene 
in the oil. The separation was not at all quantitative, as a consid- 
erable proportion was lost in the manipulations incident to the 
separation. Since the quantity of oil at hand was so meager the 
fractions were reduced to such small quantities that further separa- 
tion of crystals was impossible, and as unavoidable losses were 
encountered in transferring to and from the centrifuge the final 
percentages were materially affected and the true amount of stear- 
optene may be assumed to be considerably more than is shown above. 

After the fractionation and refractionation of the oil and the 
separation of the stearoptene portion, the remaining elaoptene portion 
grouped itself into fractions, whose physical properties were deter- 
mined and qualitative tests for their constituents applied, as shown 
in Table VI. 

235 



34 



WILD VOLATILE-OIL PLANTS, 



Table VI. — Refractionation of the oil of swamp bay, showing the physical properties of 

the fractions . 



Frac- 
tion. 




Specific 


Rotation 


Re-frac- 




Temperature. 


gravity 


in 50-mm. 


tion Nn 


Tests applied. 




at 25° C. 


tube. 


25". 






Degrees C. 




Degrees. 






1 


Below 170 


Insuffi- 


Insuffi- 


1. 4648 


When shalven with water the aqueous solution 






cient. 


cient. 




strongly reduced magenta solution to violet 
color; also produced silver mirror with am- 
moniacal silver nitrate. 


2 


170 to 182 


0.9011 


+22.5 


1.4630 


lodol (tetraiodopyrol) dissolved in oil by gentle 
warming yielded vellow crystals melting at 
115° C; cineol iodo'l melts at 112° C. 


'3 


182 to 185 


.9012 


+21.5 


1. 4628 


Treated with iodol and the yellow crystals re- 
crystallized from benzol melted sharply at 112°. 


4 


185 to 190 


. 9075 


+ 23 


1.4628 


Cineol-iodol crystals melted at 113° C. 


5 


190 10 20.'') 


.9228 


+ 31 


1.4653 


Do. 


6 


205 to 215 


.9351 




1.4706 


Negative test with iodol. 


7 


215 to 233 

233 to 200 


. 9358 
. 9300 




1.4765 
1.4830 


Do. 


8 




Oxidized with 3 per cent potassium perman- 












ganate in cold yielded camphor crystals. 



IDENTIFICATION OF THE CONSTITUENTS OF THE OIL. 

Camphor. — The compound obtained from the oil by refrigeration 
was a soft, white, granular, crystalline mass, and possessed a distinct 
camphorlike odor and slightly bitter camphoraceous taste. The 
crystals sublimed readily and melted at 174° to 176° C. The boiling 
point of the compound was 205° C, and the rotation in a 50 mm. tube 
of 20 per cent solution in alcohol was found to be +3.8°, 20 percent 
solution of commercial camphor in alcohol rotating +3.5°. It was 
readily soluble in alcohol and the other organic solvents. 

To further identify the crystals with ordinary camphor two com- 
pounds were prepared, the semicarbazone and the oxime, with which 
camphor forms definite chemical compounds. The semicarbazone 
was prepared according to the method of Tiemann. (See p. 17.) 
The crystals obtained after recrystallization from alcohol melted at 
237° to 239° C, pure camphor semicarbazone melting at 236° to 238°. 
For the preparation of the oxime Auwer's method was applied. (See 
p. 16.) Recrystallized from ether the oxime melted at 1 17° to 118° C, 
whereas pure camphor oxime melts at 118° to 119° C. 

Since the physical and chemical properties of tliis substance cor- 
respond almost identically with those of camphor, it may be safely 
stated that the crystals are those of commercial dextro camphor. 

Aldehyde constituent. — From the pungent and penetratmg odor and 
the strong reducing properties of the first fraction, wliich, as shown 
in Table V, distilled largely below 80° C, there would seem to be the 
possible presence of a trace of formaldehyde. 

Cineol, or eucalyptol. — Qualitative tests as indicated in Table V 
show the presence of cineol in fractions from 170° to 205° C, the 
characteristic crystalline cineol addition product of iodol correspond- 
ing in melting point to the pure cineol iodol. Cineol was further 

235 



SWAMP BAY. 35 

identified in these fractions by the preparation of cineol hydrobromid 
prepared by passing dry hydrobromic acid gas into a wcll-cooletl 
sohition of the oil in petroleum ether. A crystalline hydrobromid 
was obtained from each fraction which gave the iodol reaction. The 
hydrobromids prepared melted between 55° to 57° C, while pure cineol 
hydrobromid is reported as melting at 56° to 57° C. 

Since the presence of cineol in the several fractions of the oil was 
proved, a quantitative estimation was deemed desirable. Because of 
the smallness of the individual fractions the hydrobromic acid method 
was adopted in this estimation, it being the most accurate when cineol 
is present in only small quantities. The phosphoric acid method is 
best adapted to oils which are very rich in the compound. The 
hydrobromic acid method has been used in the assay of eucalyptus 
oils,^ and consists essentially in conducting dry hydrobromic acid gas 
into a solution of the oil in about twice its volume of petroleum ether, 
the solution being well cooled by a freezmg mixture, separating the 
crystals on a force filter, wasliing and decomposing with water, and 
measuring the cineol formed. A slight deviation was made from 
the directions on account of the smallness of the fractions and 
consequently the small amount of hydrobromid obtained, which 
when decomposed with water would introduce an error. After the 
hydrobromid of cineol was obtained in each case and washed it was 
weighed and the percentage of cineol was calculated from the weight 
of the crystals from a given quantity of each fraction. In tins 
manner by assaying the four fractions which gave qualitative tests 
there was found to be a total of 19.8 per cent of cineol in the oil. 

Borneol. — By oxidation of fraction 233° to 260° C. with a 3 per cent 
solution of potassium permanganate, slightly warming and allowing 
it to stand for 12 hours, then shaking out the mixture with ether and 
allowing the ether to evaporate, a mass of crystals remained which 
proved to be camphor. It is possible that borneol was present in this 
fraction, as borneol is readily oxidized to camphor with ordinary 
oxidizing agents. Since the preliminary chemical examination of 
the oil indicated a small percentage of esters and of free alcohol, the 
alcohol was probably borneol. 

SUMMARY. 

From the results obtained in the chemical examination it appears 
that the oil of swamp bay contains over 21 per cent of camphor, 19.8 
per cent cineol, and borneol, the latter possibly occurring to a small 
extent as esters and as the free alcohol. No terpenes were identified. 
Since only a very small portion of the oil distills over below 175° C, 

' Gildemeister, Eduard, and Hoffmann, Friedrich. Translated by Edward Kremers. The Volatile 
Oils, p. 528. 
235 



36 WILD VOLATILE-OIL, PLANTS. 

it would seem that the oil is not terpenic in character, as most mem- 
bers of the terpene group of hydrocarbons boil below 175° C. 

Besides the constituents mentioned, the oil contains butyric acid 
in free condition to a slight extent ; butyric, valerianic, and heptoic 
acids combined in the oil as esters, valerianic acid predominating, and 
a slight trace of an aldehyde, possibly formaldehyde. 

This oil possessing, as has been proved, considerable quantities of 
such constituents as camphor, cineol, and borneol, all of which are 
valuable therapeutic agents, may be of economic importance from the 
standpoint of the perfumer or the medical practitioner. Doubtless 
if the distillation of the plant were carried on, attention being paid to 
the stage of growth at which it is distilled and the distillation re- 
stricted to the leaves and small twigs, the yield of oil and possibly the 
yield of the three important constituents mentioned could be consider- 
ably augmented, 

CONCLUSIONS. 

The plants described in the foregoing pages and the volatile oils 
distilled from them represent but a small part of our wild aromatic 
flora, yet these plants gathered from their wild haunts have been made 
to yield products which give promise of no little economic importance. 
It is the object of this work simply to call attention to the products 
capable of being obtained from our native plants and to emphasize 
their possible application in the trades and arts. The actual growth 
and cultivation of such as prove to be of economic value should follow. 

The lands on which the rankest growth of wild plants occurs are 
usually of little value for the production of agricultural crops, and 
doubtless large areas of this character exist in all sections of the 
United States, which lands might be utilized for the growth of certain 
aromatic plants now largely classed as weeds yet which may be made 
to yield products of value. 

That there is a field for investigation in this direction is shown in 
the preceding pages in which three plants representing specimens 
picked up at random have been shown to yield oils containing large 
quantities of such important compounds as camphor, borneol, and 
cineol. Inasmuch as camphor is consumed in enormous quantities 
in the United States, the supply at present commg wholly from for- 
eign countries, the presence of such large quantities of this substance 
in the volatile oils of black sage and swamp bay should not be over- 
looked. The cultivation of these plants should not be impracticable. 
Since black sage if distilled at its flowering stage could be made to 
yield approximately 1 per cent of oil from the green plant and the oil 
in turn be made to yield from 40 to 50 per cent of camphor, its growth 
and cultivation should be profitable. Furthermore, as the plant is a 
perennial, a crop of foliage could be produced each year, and the 

235 



CONCLUSIONS. 37 

luxuriant growth of the plant, coupled with the exceptionally high 
yield of oil would produce a large amount of oil and camphor per unit 
of area. After the separation of the camphor from the oil the cam- 
phor-free oil remaining would still possess value because of its high 
content of cineol. 

The swamp bay, which yields oil and camphor, though in somewhat 
smaller quantities, should also receive attention along similar lines. 

The wild sage is an example among the wild plants of the United 
States in which borneol is found in quantity. As a natural source for 
this compound the plant is far more promising than the two plants 
native to Borneo and the Malay Archipelago, which yield most of the 
borneol of commerce, supplying a large proportion to the Chinese, 
among whom there is a brisk demand. The abundance of wild sage 
found in this country, the ease with which it might be cultivated, and 
the large percentage of borneol and cineol capable of separation from 
the oil make it a most excellent source from which to obtain these 
substances. The oil also possesses virtues as a scenting agent 
because of the high percentage of the esters of borneol, which are 
excellent perfuming materials. As a source for the production of 
bornyl acetate wliich is extensively used by perfumers for its pine- 
needle odor, this oil should prove of value. 

Since the oil from each of these plants shows important chemical 
constituents which may be commercially applied in many ways, their 
cultivation for these products is worthy of consideration. 

•235 

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0'12 



LIBRARY OF CONGRESS 



0Q00^327Tafi 




